【作者】 安丽荣；

【导师】 唐宗薰；

【作者基本信息】 西北大学 ， 无机化学， 2004， 硕士

【摘要】 糖尿病是一种与生活习惯相联系的疾病，同时也是世界上最普遍的疾病之一。科学的发展要求具有口服活性且无毒性的化合物来取代疼痛的胰岛素注射。1921年，报道了口服钒酸钠可以改善人体糖尿病。1979年，确定了V离子[V（Ⅲ），V（Ⅳ），V（Ⅴ）]的类胰岛素性质。由于在生理pH下，V（Ⅲ）很容易被氧化成V（Ⅳ）和V（Ⅴ）。V（Ⅳ）的毒性小于V（Ⅴ），氧钒态（V=0）的毒性又小于钒酸态(VO₃^-1)的毒性。故本论文就围绕V（Ⅳ）和V（Ⅴ）的几个氧钒配合物展开研究。 第一章对氧钒配合物的研究现状进行综述。 第二章叙述本论文所用到的程序。 第三章运用Gaussian 98量子化学程序，在B3LYP／LANL2DZ水平上，对六个+4价的氧钒配合物VO（ma）₂、VOPA、VO（opt）₂、tran-VCME、VO（metf）₂、VO（S₂CN（CH₃）₂）₂进行了几何构型优化及相应性质的计算。为进一步比较，在同一条件下，对另两个配合物cis-VCME，VOPA的取代衍生物VOMPA做了同样的说明。后又采用Gaussian 03量化程序，对上述六个配合物在ONIOM（B3LYP／LANL2DZ：UFF）水平上进行了分层计算。 第四章分别在B3LYP／LANL2DZ，B3LYP／6-31G*和HF／6-31G*的水平上对联麦氧钒配合物VO（ma）₂（C₁）及其氧化产物cis-[VO（OCH₃）（ma）₂]（C₂）和cis-[VO（ma）₂O]^-（C₃）进行了几何构型全优化及相应性质的计算。 第五章报道配合物[VO（PA）₂]（PA=吡啶羧酸）及其配体中吡啶环上取代基效应的量子化学密度泛函（DFT）研究的结果。 第六章使用Gaussian 98程序，采用密度泛函理论DFT中的B3LYP方法和有效势LANL2DZ基组，对bpV（phen）、bpV（bipy）、bpV（pic）、bpV（NH₃）₂、bpV（ox）和bpV（NH₃）六个氧钒配合物进行理论计算。 第七章附加了在B3LYP／LANL2DZ和HF-SCF／LANL2DZ两个水平上，对铂的配合物2，6-（R₂PCH₂）₂C₆H₃PtX（R=Me，Et，Ph，t-Bu；x=Cl，Br）进行的几何构型全优化及频率分析。为了进一步考查环的大小和构型对这类配合物性质的影响，还对配合物2，6-（Ph₂PCH₂CH₂）₂C₆H₃PtX（X=Cl，Br）作了相关计算，并与上述八个配合物进行了比较。更多还原

【Abstract】 Diabetes mellitus (DM) is one of the life style-related diseases as well as one of the most widespread diseases in the world. The development is required of orally active compounds and that of compounds without side effects in place of painful insulin injections. In 1921, orally administrated sodium vanadate was reported to improve DM in human diabetes. The in vitro insulin-mimetic effect of vanadium ions was confirmed later in 1979. Because V(III) is readily oxidized to V(IV) and V(V) at physio-logical pH and V(IV) is less toxic than V(V), V = O is also less toxic than VO3 -1, this paper have investigated several oxovanadium(IV) and oxovanadium (V) complexes.At chapter 1, the investigation actuality of oxovanadium complex has been summarized.At chapter 2, The program used is recited in this paper.At chapter 3, the complexes of Oxovanadium(IV): VO(ma)2, VOPA, V0(opf)2, tran-VCME, VO(metf)2, VO(S2CN(CH3)2)2 were studied with DFT by means of Gaussian 98 and with ONIOM by means of Gaussian 03. In order to compare, the complexes of cis-VCME and VOMPA were also studied in the same level.At chapter 4, the complexes VO(ma)2 and its oxidation producetions cis-[VO(ma)2O]- and cis-VO(OCH3)(ma)2 were studied with DFT and HF by means of Gaussian 98 package.At chapter 5, the studies on the complex VO(PA)2 and its substitution derivates on Py werecarried out with DFT. The regularities of the substituent( - CH3, - CH(CH3)2, -I, - Cl) effectson affecting the stability of the complexes have been investigated.At chapter 6, the studies on the oxovanadium complexes bpV(phen), bpV(bipy), bpV(pic), bpV(NH3)2, bpV(ox) and bpV(NH3) were carried out with DFT.At chapter 7, the studies on the complexes of 2, 6-bis[(R2phosphino)methyl]-Platinum-X (R =Me, Et, Ph, t-Bu; X=C1, Br)and2,6-bis-[(Ph2phosphino)ethyl]-Platinum-X(X=Cl,Br) were carried out with DFT at B3LYP/LANL2DZ level and with HF method at HF-SCF/LAN L2DZ level by means of Gaussian 98 package.更多还原